CN102633497B - The biphase ceramics of dicalcium phosphate pottery, dicalcium phosphate and oxyhydrogen-base apatite and manufacture method thereof - Google Patents

The biphase ceramics of dicalcium phosphate pottery, dicalcium phosphate and oxyhydrogen-base apatite and manufacture method thereof Download PDF

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CN102633497B
CN102633497B CN201210034609.1A CN201210034609A CN102633497B CN 102633497 B CN102633497 B CN 102633497B CN 201210034609 A CN201210034609 A CN 201210034609A CN 102633497 B CN102633497 B CN 102633497B
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oxyhydrogen
dicalcium phosphate
base apatite
ceramic
biphase ceramics
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CN102633497A (en
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刘松村
陈松青
赖慧君
黄琬婷
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Hekang Biological Sci & Tech Co Ltd
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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/447—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on phosphates, e.g. hydroxyapatite
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/12—Phosphorus-containing materials, e.g. apatite
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/56—Porous materials, e.g. foams or sponges
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
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    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/12—Materials or treatment for tissue regeneration for dental implants or prostheses
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
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    • C04B2235/606—Drying

Abstract

The invention discloses the method for biphase ceramics of a kind of manufacture pure phosphoric acid dicalcium pottery for the medical applications at sclerous tissues position or dicalcium phosphate and oxyhydrogen-base apatite, so that being used as embedded material. These pottery embedded materials are graininess or bulk, and by use one acid phosphatase salt compound, one include the basic calcium phosphate compound of oxyhydrogen-base apatite and water and prepare. This dicalcium phosphate pottery includes dicalcium phosphate dihydrate (CaHPO4��2H2O, DCPD) or anhydrous dicalcium phosphate (CaHPO4, DCPA). Wherein when the stoichiometry of the acid phosphatase salt compound provided equals or exceeds basic calcium phosphate compound, product is DCPD ceramic or DCPA ceramic; When the stoichiometry of the acid phosphatase salt compound provided is less than basic calcium phosphate compound, product is the biphase ceramics of the dicalcium phosphate dihydrate biphase ceramics with oxyhydrogen-base apatite or anhydrous dicalcium phosphate and oxyhydrogen-base apatite.

Description

The biphase ceramics of dicalcium phosphate pottery, dicalcium phosphate and oxyhydrogen-base apatite and manufacture method thereof
Technical field
The present invention relates to a kind of new biology can the manufacture method of resorbent calcium phosphate ceramic, a kind of method particularly relating to biphase ceramics manufacturing and being suitable for the dicalcium phosphate pottery as bone grafting material, bone substitute and bone filler and dicalcium phosphate and oxyhydrogen-base apatite (hydroxyapatite, HA).
Background technology
Inorganic constituents main in sclerous tissues is biogenic apatite. For example, bone contain 65% to close to 70% biogenic apatite, tooth then contains the biogenic apatite higher than 98%. Oxyhydrogen-base apatite (hydroxyapatite, HA) is a kind of to have and the calcium phosphate compound of biogenic apatite similar crystal structure. In principle, oxyhydrogen-base apatite should be the ideal chose of hard tissue alternate material. But, the oxyhydrogen-base apatite (precipitatedHA) of precipitation is very thin powder, and due to operational difficulty, this is using the application as hard tissue alternate material of the oxyhydrogen-base apatite that hinders precipitation. The calcium phosphate particles of other precipitation there is also similar problem, for instance the medical applications of dicalcium phosphate.
At the initial stage in the 1980's, it is attempted to be prepared the calcium phosphate ceramic of graininess or bulk by ceramic sintering technology. At about 30 years of the past, it is made for many types of calcium phosphate ceramic. In these potteries, oxyhydrogen-base apatite, ��-and bata-tricalcium phosphate (tricalciumphosphate, TCP) pottery are widely studied. Clinical research confirmation, major part has calcium/phosphorus mol ratio calcium phosphate ceramic such as dicalcium phosphate, oxyhydrogen-base apatite equal to one or higher, tricalcium phosphate and tetracalcium phosphate (tetracalciumphosphate, TTCP) there is the bio-compatibility of excellence, and can be accepted well by sclerous tissues and soft tissue. Experimental result points out that the oxyhydrogen-base apatite of densification is not resorbable, and other porous calcium phosphate ceramic is then resorbable. It is said that in general, the re-absorption speed ratio oxyhydrogen-base apatite of bata-tricalcium phosphate pottery is faster, but mechanical strength is more weak than oxyhydrogen-base apatite. In order to obtain the pottery of mechanical performance and the bioresorbable that can be well combined, a kind of biphasic calcium phosphate (biphasiccalciumphosphate, BCP) pottery is produced, and these biphase ceramics are the mixture of oxyhydrogen-base apatite and bata-tricalcium phosphate. Above-mentioned most pottery is not resorbent is exactly be difficult to control to its non-bioresorbable speed too slowly.
First Brown and Chow delivered the calcium phosphate of bone cement (cement) kenel as medical applications in 1986. The main composition of this bone cement is tetracalcium phosphate and dicalcium phosphate, and main product is oxyhydrogen-base apatite. After that, the calcium phosphate bone cement with different formulations is had been developed in. The major advantage of calcium phosphate bone cement is its plasticity. The calcium phosphate bone cement developed can be complied with its product and be classified, substantially, calcium phosphate bone cement has two main Types, that is oxyhydrogen-base apatite bone cement and dicalcium phosphate dihydrate (dicalciumphosphatedihydrate, DCPD) bone cement. Similar in appearance to high temperature hydrogen oxyapatite, the re-absorption speed of oxyhydrogen-base apatite bone cement is very slow. The main composition of dicalcium phosphate dihydrate is basic calcium phosphate such as type alpha tricalcium phosphate, bata-tricalcium phosphate or oxyhydrogen-base apatite, and acid phosphatase salt compound such as phosphoric acid or one-lime phosphate, and some curing solutions. It is said that in general, the bone cement acidity of this type is quite strong, and except product is dicalcium phosphate dihydrate, also comprise a large amount of unreacted composition. Physics and the chemical property of this type bone cement also vary widely, such as when using bata-tricalcium phosphate to prepare dicalcium phosphate dihydrate bone cement, always maintain excessive a lot of basic calcium phosphate, additionally, also always retain some crystal growth inhibitors to control hardening time. After solidification, except the dicalcium phosphate dihydrate formed, also comprise those excessive unreacted compositions and the reagent of some regulation and control solidifications. On the other hand, if the amount that use stoichiometry is fixed, then the acidity solidifying bone cement can cannot use too by force. If using oxyhydrogen-base apatite rather than tricalcium phosphate, its hardening time will be difficult to control to, and the acidity solidifying bone cement is too strong. Similar in appearance to the oxyhydrogen-base apatite of precipitation, the dicalcium phosphate prepared through intermediate processing is also fine powder and has operational problem. Even if the purity of this powder is significantly high, still can not use as bone filler or bone substitute due to its operational problem.
In recent years, calcium sulfate was also normally used as bone filler or alternate material. But, quick non-bioresorbable speed and low-intensity are its main shortcomings, and this also makes it unsuitable for for bigger Cranial defect or when the time of union of fracture is all more than 4 to 6. Saying from practical standpoint, the bioceramic as bone filler or bone alternate material should possess controllable physics and chemical property, for instance mechanical strength and non-bioresorbable speed.
Calcium phosphate compound has many types, wherein there are dicalcium phosphate, calcium pyrophosphate, type alpha tricalcium phosphate, bata-tricalcium phosphate, oxyhydrogen-base apatite and tetracalcium phosphate, some of which compound is prepared only by high-temperature technology, such as tetracalcium phosphate and type alpha tricalcium phosphate, some can only be formed with intermediate processing, such as dicalcium phosphate dihydrate and anhydrous dicalcium phosphate (DCPA). Other calcium phosphate mineral such as oxyhydrogen-base apatite, apatite mineral and calcium pyrophosphate etc. all can be prepared by high temperature sintering technique or intermediate processing. In order to medical applications is as bone substitute or bone filler, most calcium phosphate ceramic all makes graininess or bulk by high temperature sintering technique. For example, commercially available medical calcium phosphate ceramic is block or granular oxyhydrogen-base apatite, bata-tricalcium phosphate or the biphasic calcium phosphate comprising both oxyhydrogen-base apatite and bata-tricalcium phosphate. The always very thin powder of calcium phosphate compound of precipitation, therefore due to operational difficulty, the calcium phosphate material of precipitation is restricted as the application of bone substitute or bone filler. Pure dicalcium phosphate dihydrate is prepared typically by intermediate processing, anhydrous dicalcium phosphate then can by intermediate processing or by dicalcium phosphate dihydrate under high temperature dehydration and obtain. The dicalcium phosphate prepared by the method is also very thin powder, and has any problem in the field for bone collection or bone filler. Granular dicalcium phosphate can be prepared by granulating technique, but always contains adhesive in the process of preparation. Additionally, the granule prepared by granulating technique is not strong. These reasons make the dicalcium phosphate of precipitation have any problem for sclerous tissues position.
Additionally, dicalcium phosphate dihydrate close to precipitation in 4 or less calcium phosphate saturated solution can be at pH value it is well known that but when the pH of calcium phosphate saturated solution is for during close to 7 or higher, the calcium phosphate of precipitation is oxyhydrogen-base apatite or apatite mineral.
Therefore, above-mentioned most bone cement or pottery all have certain disadvantages. It is an object of the invention to prepare pure phosphoric acid dicalcium (no matter two water or anhydrous) and with the compound mixture of oxyhydrogen-base apatite for medical applications, particularly in the field of bone substitute or bone filler to overcome above-mentioned shortcoming.
Summary of the invention
Therefore, a kind of method that it is an object of the invention to provide biphase ceramics manufacturing dicalcium phosphate pottery and dicalcium phosphate and oxyhydrogen-base apatite (HA), those potteries have excellent bio-compatibility and controllable non-bioresorbable speed, it is adaptable to the application of plastic surgery, oral maxillofacial surgery and dentistry.
According to the purpose of the present invention, one is provided to manufacture the biphase ceramics of dicalcium phosphate dihydrate (DCPD) pottery, anhydrous dicalcium phosphate (DCPA) pottery, dicalcium phosphate dihydrate and oxyhydrogen-base apatite (DCPD/HA) or the method for the biphase ceramics of anhydrous dicalcium phosphate and oxyhydrogen-base apatite (DCPA/HA), comprising the steps of formation one mixture, this mixture contains an acid phosphatase salt compound and and includes the basic calcium phosphate compound of oxyhydrogen-base apatite; Add in water so far mixture to form a pastel; Mould this pastel and become a required form, and this pastel that hardens is to obtain a solid material; Clean and lixiviation (leaching) solid material is until the surface p H of this solid material reaches 4.5 or higher; And room temperature or lower than 95 DEG C at this solid material dry to obtain the biphase ceramics of DCPD ceramic or dicalcium phosphate dihydrate and oxyhydrogen-base apatite, or at the temperature of 100 DEG C or higher, dry this solid material to obtain the biphase ceramics of DCPA ceramic or anhydrous dicalcium phosphate and oxyhydrogen-base apatite. Wherein, when the stoichiometry of the acid phosphatase salt compound provided equals or exceeds basic calcium phosphate compound, its product is DCPD ceramic or DCPA ceramic; When the stoichiometry of the acid phosphatase salt compound provided is less than basic calcium phosphate compound, product is then the biphase ceramics of the dicalcium phosphate dihydrate biphase ceramics with oxyhydrogen-base apatite or anhydrous dicalcium phosphate and oxyhydrogen-base apatite.
It is preferred that basic calcium phosphate compound is except comprising oxyhydrogen-base apatite, also comprise tricalcium phosphate, calcium carbonate, calcium oxide, calcium hydroxide or its combination.
It is preferred that acid phosphatase salt compound comprises a water one-lime phosphate (monocalciumphosphatemonohydrate), anhydrous phosphoric acid one calcium, phosphoric acid or its combination.
It is preferred that the biphase ceramics of the biphase ceramics of DCPD ceramic, DCPA ceramic, dicalcium phosphate dihydrate and oxyhydrogen-base apatite or anhydrous dicalcium phosphate and oxyhydrogen-base apatite is graininess or bulk.
It is preferred that dicalcium phosphate dihydrate and the biphase ceramics of oxyhydrogen-base apatite or the biphase ceramics of anhydrous dicalcium phosphate and oxyhydrogen-base apatite include the dicalcium phosphate mineral of the percentage by weight of about 30% to about 95% and the oxyhydrogen-base apatite of the percentage by weight of about 5% to about 70%.
In addition, the present invention further provides the bioceramic of a kind of medical applications for sclerous tissues position, be selected from a DCPD ceramic manufactured by such as said method, group that DCPA ceramic, dicalcium phosphate dihydrate form with the biphase ceramics of oxyhydrogen-base apatite and the biphase ceramics of anhydrous dicalcium phosphate and oxyhydrogen-base apatite.
It is preferred that the biphase ceramics of the biphase ceramics of DCPD ceramic, DCPA ceramic, dicalcium phosphate dihydrate and oxyhydrogen-base apatite or anhydrous dicalcium phosphate and oxyhydrogen-base apatite is the bulk with a pore space structure (porousstructure).
In brief, biphase ceramics and manufacture method thereof according to the dicalcium phosphate pottery of the present invention, dicalcium phosphate and oxyhydrogen-base apatite can provide one or more following advantage:
(1) this exercising ordinary skill all to know solubility more high, Ksp value is more high. At 25 DEG C, the Ksp value of anhydrous dicalcium phosphate is 1 �� 10-6.90; Dicalcium phosphate dihydrate Ksp value is 1 �� 10-6.59; The Ksp value of type alpha tricalcium phosphate (��-TCP) is 1 �� 10-25.5; The Ksp value of bata-tricalcium phosphate (��-TCP) is 1 �� 10-28.9; And the Ksp value of oxyhydrogen-base apatite is 1 �� 10-116.8(DentMaterJ2009; 28 (1): 1-10). It addition, the Ksp value of calcium sulfate is 9.1 �� 10 at 25 DEG C-6. Therefore, according to the dicalcium phosphate of present invention pottery, namely dicalcium phosphate dihydrate (CaHPO4��2H2And anhydrous dicalcium phosphate (CaHPO O)4) pottery both, have lower than calcium sulfate but higher than the solubility of tricalcium phosphate (TCPs) and oxyhydrogen-base apatite. In other words, it is contemplated that this little dicalcium phosphates pottery and will provide for splendid bio-compatibility with the combination of oxyhydrogen-base apatite, and have and be slower than calcium sulfate but faster than the non-bioresorbable speed of oxyhydrogen-base apatite and tricalcium phosphate.
(2) those dicalcium phosphates/oxyhydrogen-base apatite biphase ceramics of the present invention, namely the biphase ceramics of the biphase ceramics of dicalcium phosphate dihydrate and oxyhydrogen-base apatite and anhydrous dicalcium phosphate and oxyhydrogen-base apatite, can contain dicalcium phosphate mineral (i.e. dicalcium phosphate dihydrate and anhydrous dicalcium phosphate) and the oxyhydrogen-base apatite of different proportion according to required non-bioresorbable speed. Additionally, the biphase ceramics of this little dicalcium phosphates pottery and dicalcium phosphate and oxyhydrogen-base apatite can be made into graininess or bulk, and by using different reagent optionally to have pore space structure. Therefore, the present invention provide a kind of biology can resorbent Novel phosphoric acid calcium pottery, can pass through to adjust dicalcium phosphate mineral and the ratio of oxyhydrogen-base apatite, the kind of reagent, the type of solid-type or the quantity of hole and size and have controllable non-bioresorbable speed. It is to say, the present invention according to the part of the sclerous tissues of needs reparation and region, can control the non-bioresorbable speed of the biphase ceramics of this little dicalcium phosphates pottery and dicalcium phosphate and oxyhydrogen-base apatite.
(3) have close to neutral pH (about 4.5 or higher according to this little dicalcium phosphates pottery of the present invention and the biphase ceramics of dicalcium phosphate and oxyhydrogen-base apatite, it is preferably 5 to 6.5), so these potteries will not cause the side effect such as stimulation or inflammatory response after the implants.
The other side of the present invention will be allocated as explanation in the middle part of being described in detail subsequently, and eligibly think deeply through its teaching work part or understood by disclosed embodiment of this invention. The every aspect of the present invention can pass through the composition and combination that are particularly pointed out in claims below and be understood and complete. It is noted that the above-mentioned summary of the present invention and the following detailed description are demonstration and the effect illustrated, but not it is used for limiting scope of the invention.
Accompanying drawing explanation
Fig. 1 is the flow chart of the method manufacturing DCPD ceramic according to the first embodiment of the present invention.
Fig. 2 is the flow chart of the method manufacturing DCPA ceramic according to the second embodiment of the present invention.
Fig. 3 is the flow chart manufacturing dicalcium phosphate dihydrate and the method for the biphase ceramics of oxyhydrogen-base apatite according to the third embodiment of the invention.
Fig. 4 is the flow chart manufacturing anhydrous dicalcium phosphate and the method for the biphase ceramics of oxyhydrogen-base apatite according to the fourth embodiment of the invention.
Fig. 5 is the XRD figure showing the dicalcium phosphate dihydrate according to one embodiment of the invention with the biphase ceramics of oxyhydrogen-base apatite.
Primary clustering symbol description
S11��S15: step
S21��S25: step
S31��S35: step
S41��S45: step
Detailed description of the invention
Coordinating accompanying drawing and the further detail below of various embodiments of the invention, the one exemplary embodiment of the present invention will be understood more fully.
With reference to Fig. 1, it is the manufacture dicalcium phosphate dihydrate (CaHPO according to the first embodiment of the present invention4��2H2O, DCPD) flow chart of method of pottery. The method comprises the steps of in step s 11, form a mixture, this mixture contains the basic calcium phosphate compound that an acid phosphatase salt compound and includes oxyhydrogen-base apatite (HA), and the stoichiometry of the acid phosphatase salt compound wherein provided equals or exceeds basic calcium phosphate compound. In step s 12, add water to form a pastel in this mixture. In step s 13, by this pastel mold or mould and become a required form, and harden to obtain a solid material. In step S14, this solid material is cleaned and lixiviation is until its surface p H reaches about 4.5 or higher, it is advantageous to be 5 to 6.5. In step S15, this solid material is placed in room temperature or dry to obtain DCPD ceramic at lower than 95 DEG C.
With reference to Fig. 2, it is manufacture anhydrous dicalcium phosphate (CaHPO according to the second embodiment of the present invention4, DCPA) and the flow chart of method of pottery. The method comprises the steps of in the step s 21, obtain a mixture, this mixture contains an acid phosphatase salt compound and and includes the basic calcium phosphate compound of oxyhydrogen-base apatite, and the stoichiometry of the acid phosphatase salt compound wherein provided equals or exceeds basic calcium phosphate compound. In step S22, add water to form a pastel in this mixture. In step S23, by this pastel mold or mould and become a required form, and harden to obtain a solid material. In step s 24, this solid material is cleaned and lixiviation is until its surface p H reaches about 4.5 or higher, it is advantageous to be 5 to 6.5. In step s 25, it is dry to obtain DCPA ceramic to be placed in by this solid material at the temperature of 100 DEG C or higher.
With reference to Fig. 3, it is the flow chart manufacturing dicalcium phosphate dihydrate and the method for the biphase ceramics of oxyhydrogen-base apatite according to the third embodiment of the invention. The method comprises the steps of in step S31, form a mixture, this mixture contains an acid phosphatase salt compound and and includes the basic calcium phosphate compound of oxyhydrogen-base apatite, and the stoichiometry of the acid phosphatase salt compound wherein provided is less than basic calcium phosphate compound. In step s 32, add water to form a pastel in this mixture. In step S33, by this pastel mold or mould and become a required form, and harden to obtain a solid material. In step S34, this solid material is cleaned and lixiviation is until its surface p H reaches about 4.5 or higher, it is advantageous to be 5 to 6.5. In step s 35, this solid material is placed in room temperature or lower than 95 DEG C at the dry biphase ceramics to obtain dicalcium phosphate dihydrate and oxyhydrogen-base apatite.
With reference to Fig. 4, it is the flow chart manufacturing anhydrous dicalcium phosphate and the method for the biphase ceramics of oxyhydrogen-base apatite according to the fourth embodiment of the invention. The method comprises the steps of in step S41, obtain a mixture, this mixture contains an acid phosphatase salt compound and and includes the basic calcium phosphate compound of oxyhydrogen-base apatite, and the stoichiometry of the acid phosphatase salt compound wherein provided is less than basic calcium phosphate compound. In step S42, add water to form a pastel in this mixture. In step S43, by this pastel mold or mould and become a required form, and harden to obtain a solid material. In step S44, this solid material is cleaned and lixiviation is until its surface p H reaches about 4.5 or higher, it is advantageous to be 5 to 6.5. In step S45, this solid material is placed at the temperature of 100 DEG C or higher and dries the biphase ceramics to obtain anhydrous dicalcium phosphate and oxyhydrogen-base apatite.
Description according to above-described embodiment, after step S13, S23, S33 or S43, this solid material can be dry at room temperature is to about 90 DEG C. Basic calcium phosphate compound can have the calcium more than 1/phosphorus mol ratio, and acid phosphatase salt compound can have the calcium less than 1/phosphorus mol ratio. Or, basic calcium phosphate compound, except comprising oxyhydrogen-base apatite, more can comprise tricalcium phosphate (TCP), calcium carbonate, calcium oxide, calcium hydroxide or its combination. Acid phosphatase salt compound can comprise a water one-lime phosphate (Ca (H2PO4)2��H2O, MCPM), anhydrous phosphoric acid one calcium (Ca (H2PO4)2, MCPA), phosphoric acid or its combination.
It addition, the stoichiometry of the acid phosphatase salt compound provided can the excessive percentage by weight of about 0.1% to about 20%, in order to obtain DCPD ceramic or DCPA ceramic. The purity of DCPD ceramic or DCPA ceramic can be at least 97%. The oxyhydrogen-base apatite used can be the oxyhydrogen-base apatite (precipitatedHA) of the oxyhydrogen-base apatite (sinteredHA) sintered or precipitation. The particle diameter of the oxyhydrogen-base apatite used can be complied with different demands and design, for instance can be particle size range in the powder of about 0.1 millimeter to about 2 millimeters or graininess. In addition, the biphase ceramics of the biphase ceramics of DCPD ceramic, DCPA ceramic, dicalcium phosphate dihydrate and oxyhydrogen-base apatite or anhydrous dicalcium phosphate and oxyhydrogen-base apatite can be graininess and its preferably particle size range is at about 0.1 millimeter to about 5 millimeters, or for block and be preferably there is pore space structure. Dicalcium phosphate dihydrate and the biphase ceramics of oxyhydrogen-base apatite or the biphase ceramics of anhydrous dicalcium phosphate and oxyhydrogen-base apatite can include the dicalcium phosphate mineral of the percentage by weight of about 30% to about 95% and the oxyhydrogen-base apatite of the percentage by weight of about 5% to about 70%.
In another embodiment, the mixture formed more comprises porogen (porogen), such as sodium chloride, potassium chloride, maltose, sucrose or its combination.
In other embodiments, the biphase ceramics of DCPD ceramic, DCPA ceramic, dicalcium phosphate dihydrate and oxyhydrogen-base apatite or the biphase ceramics of anhydrous dicalcium phosphate and oxyhydrogen-base apatite are provided according to said method and content.
The present invention provides and is in granular form or the low temperature calcium phosphate ceramic of bulk, and it contains the combination of almost pure dicalcium phosphate or dicalcium phosphate and oxyhydrogen-base apatite. These a little potteries are suitable for the material as bone collection or bone filler. This dicalcium phosphate can be dicalcium phosphate dihydrate or anhydrous dicalcium phosphate one of them. Granular pottery can have and is sized to about 0.1 millimeter to about 5 millimeters irregularly shaped. Block pottery can be spherical or other shape, it is possible to prepare for having pore space structure. The pottery of the present invention is the bone filler being suitable for or a bone substitution material, and it has and is slower than Gypsum Fibrosum preparata (PlasterofParis) but faster than the non-bioresorbable speed of oxyhydrogen-base apatite or tricalcium phosphate.
The present invention can use oxyhydrogen-base apatite and one-lime phosphate or phosphoric acid as the reacted constituent of the biphase ceramics preparing dicalcium phosphate pottery or dicalcium phosphate and oxyhydrogen-base apatite. For obtaining pure dicalcium phosphate pottery, the calcium of parent material/phosphorus mol ratio is less than 1 or close to 1. As for the biphase ceramics of dicalcium phosphate Yu oxyhydrogen-base apatite, its calcium/phosphorus mol ratio is then more than 1. But, wherein do not comprise any solidification regulator. In current preparation process, hardening time is not main Consideration. After solidification, bulk or spheroidal material are immersed in pure water for several times, until the final water soaked presents close to 5 or close to neutral pH value. As possessed pore space structure, then curing powder can comprise organic solid or the inoganic solids of available water lixiviation, for instance sugar, sodium chloride or maltose. After solidification, then by this soluble material lixiviation out to cause pore space structure. When producing granular material, the solid material of solidification is smashed and is sieved to obtain the granule of required size to pieces. Similar to producing bulk material, those granules are immersed in pure water for several times, until the final water soaked presents close to 6 or close to neutral pH value. Then by air-dry for above-mentioned pottery or dry with the heating temperatures lower than 100 DEG C, to obtain the biphase ceramics of DCPD ceramic or dicalcium phosphate dihydrate and oxyhydrogen-base apatite. As for DCPA ceramic, then it is to carry out the dehydration of enough time at the temperature of 100 DEG C or higher by above-mentioned pottery, to guarantee dicalcium phosphate dihydrate is changed into anhydrous dicalcium phosphate. Control the flexibility ratio of non-bioresorbable speed when these potteries can provide medical, and rational mechanical strength is provided.
In the preparation of pure dicalcium phosphate dihydrate, the basic calcium phosphate compound used can be tricalcium phosphate or oxyhydrogen-base apatite one of them. But, because hardening time is slow and is easier to the characteristic controlled, makes oxyhydrogen-base apatite become and more suitably select. As for acid phosphatase salt compound, one-lime phosphate (anhydrous or a water (monohydrate) all can) or phosphoric acid can be used. Unlike the preparation of ordinary calcium phosphate cement, acid phosphatase salt compound can maintain at least with the mol ratio of basic calcium phosphate compound equivalent, it is advantageous to for excessive acid phosphatase salt compound. In this case, it will have enough or more acid phosphatase salt compound so that basic calcium phosphate compound complete reaction. After mixed superphosphate compound with basic calcium phosphate compound, add enough water and continue mixing until forming an available pastel. In order to obtain strong solidification solid material, the use of water should maintain the situation of the best, if with water excess, then solidifying solid material can relatively fragility. Then pastel is fashioned into the form needed for required shape or mold one-tenth. Owing to hardening time is not key element in the preparation process of pure phosphoric acid dicalcium, it is hardening that user can wait until that product is fully cured. When material solidifies not long ago, a needle-shaped tool can be used to solidify in solid material at this and to cause pore space structure.
For example, as shown in the reaction equation of lower section, if using oxyhydrogen-base apatite and one-lime phosphate in the preparation of DCPD ceramic, then can use the one-lime phosphate of excessive several % extremely excessive percentage by weight of about 20%. In order to carry out mixing more preferably, first initial reactant ground or use fine powder. Then the powder mixed is added enough water and is mixed to form an available pastel, then this pastel is cast or molded into required shape. After pastel is hardening, first this is solidified solid material air-dry or dry at the temperature lower than 90 DEG C, then by dry solid material pure water lixiviation. Or, lixiviation process can also be made directly under not being dried status of processes. This solidifies solid material can have highly acid because of excessive acid ingredient, but owing to acid ingredient solubility is strong, and the acid ingredient being embedded after solidification can pass through to solidify in solid material immersion pure water lixiviation easily out. In lixiviation process, it is proposed that change lixiviation water once in a while. When the pH value of final lixiviation liquid is close to 5, it is advantageous to time between 5 and 6.5, namely lixiviation process completes. Then by air-dry for the dicalcium phosphate dihydrate of this solid shape to obtain end product. Additionally, the oxyhydrogen-base apatite used can for the oxyhydrogen-base apatite of precipitation or both oxyhydrogen-base apatites of sintering, but, if desired stronger dicalcium phosphate, the oxyhydrogen-base apatite then sintered can be preferably select, because the water required when making pastel is less. The solidification solid dicalcium phosphate dihydrate being eventually fabricated can be arbitrary form, for instance block, cylindric or any irregular shape.
Ca5(PO4)3OH+2Ca(H2PO4)2+13H2O��7CaHPO4��2H2O
HAMCPADCPD
Preparing particle diameter in the process of the pure dicalcium phosphate dihydrate of graininess of about 0.1 millimeter to about 5 millimeters, can further smash above-mentioned dry solid product to pieces sieve to obtain required size granular materials. Another obtains the alternative method of graininess DCPD ceramic for first to be smashed to pieces by solidification solid material before being carried out and dry, after smashing to pieces and sieving, is carried out and lixiviation by selected granule according to the process preparing bulk. If desired pure anhydrous dicalcium phosphate, then by dry bulk or granule dicalcium phosphate dihydrate, dehydration under 100 DEG C or slightly higher temperature completes until dehydration. Those the block or granular pure dicalcium phosphate dihydrates made or anhydrous dicalcium phosphate should have the application with satisfied medical treatment of splendid bio-compatibility and goodish mechanical strength.
In the dicalcium phosphate dihydrate preparation with the biphase ceramics of oxyhydrogen-base apatite, outside excessive basic calcium phosphate compound oxyhydrogen-base apatite, all carry out according to similar step. The oxyhydrogen-base apatite used in this processing procedure can be fine powder, graininess or its mixing. In this case, initial cure component is still acidity. Then this cure component water continuing to change is carried out lixiviation, until the pH value of lixiviation liquid is close to 5, it is advantageous to being 5 to 6.5, all the other steps are all similar to preparing pure DCPD ceramic. The biphase ceramics of the dicalcium phosphate dihydrate being eventually fabricated and oxyhydrogen-base apatite can contain the oxyhydrogen-base apatite of the percentage by weight of about 5% to about 70% and the dicalcium phosphate dihydrate of the percentage by weight of about 95% to about 30%. In preparing the process of biphase ceramics of dicalcium phosphate dihydrate and oxyhydrogen-base apatite, from two water to anhydrous dehydration by according to the step identical with preparing pure DCPA ceramic.
In some cases, the basic calcium phosphate compound that part uses can replace with calcium carbonate, calcium hydroxide or calcium oxide. The product with pore space structure can pass through to produce with the oxyhydrogen-base apatite of calcium carbonate replacement part, it is possible to produces by including solvable organic or inorganic compound in preparation process in. Solvable inorganic compound such as potassium chloride and sodium chloride, and solvable Organic substance such as the example of the sugared material all applying to this preparation process with maltose. There is the pore space structure that the block composite material (i.e. biphase ceramics) of pore space structure produces also by the mechanically actuated using needle-shaped tool to have about 0.3 millimeter to about 1.5 millimeters of aperture.
Embodiment
Embodiment 1
By 6 grams of oxyhydrogen-base apatites (particle diameter is less than 105 microns) sintered and 8 gram of one water one-lime phosphate (Ca (H2PO4)2��H2O, MCPM) mixing, then this mixture is added enough water to form pastel. About 30 minutes are solidified to obtain a solid material after this pastel is fashioned into bulk. This solid material is carried out lixiviation with 50 milliliters every time, and is repeatedly performed lixiviation step until the surface p H of solid material is about 5.5. By air-dry for this solid material to obtain a block product. X ray research points out that this product is shown as pure dicalcium phosphate dihydrate (DCPD) pottery. Its surface p H is close to neutral. Further, a part for this block product smashed to pieces and pass through a screen cloth to collect the size granule at 5 to 35 meshes (mesh).
By be in granular form or the pure DCPD ceramic of bulk to insert temperature be in 100 DEG C or slightly higher stove, place overnight to obtain anhydrous dicalcium phosphate (DCPA) pottery.
Embodiment 2
By 4 grams of oxyhydrogen-base apatites (particle diameter is less than 150 microns) sintered and 4.5 grams of anhydrous phosphoric acid one calcium (Ca (H2PO4)2, MCPA) and the sucrose mixing of 3 grams, then this mixture is added enough water to form pastel. This pastel is placed in room temperature until it becomes a hardening solid material. This solid material is repeatedly performed lixiviation with about 50 ml pure waters every time, until the surface p H of this solid material is close to 5.5. By air-dry for the solid material after final lixiviation to obtain a product with good pore space structure. X ray shows that this product is pure DCPD ceramic. A part for this pure DCPD ceramic is smashed to pieces and sieves to collect the DCPD ceramic granule that size is at 0.5 millimeter to about 3 millimeters.
Embodiment 3
By 2 grams of oxyhydrogen-base apatites (size by 150 meshes) sintered and 0.6 gram of one water one-lime phosphate (Ca (H2PO4)2��H2O, MCPM) it is mixed and added into 0.7 gram of pure water to form pastel. Solidify after this pastel is fashioned into a rectangle about 25 minutes and obtain a solid material with this pastel that hardens. After solidification, this hard solids material is placed in air a few hours. Afterwards this solid material with pure water lixiviation and is cleaned for several times, and be repeatedly performed this lixiviation with cleaning step until the surface p H of solid material is close to 6 or lower slightly. Biphase ceramics by air-dry for the solid material after this final lixiviation dicalcium phosphate dihydrate Yu oxyhydrogen-base apatite to obtain weight 2.8 grams and density 2.52 grams per milliliter.
It is in 100 DEG C or slightly higher stove that the biphase ceramics of dicalcium phosphate dihydrate Yu oxyhydrogen-base apatite is inserted temperature, places overnight to obtain the biphase ceramics of anhydrous dicalcium phosphate and oxyhydrogen-base apatite.
Embodiment 4
By 2 grams of oxyhydrogen-base apatites (size by 150 order numbers) sintered and 0.4 gram of one water one-lime phosphate (Ca (H2PO4)2��H2O, MCPM) it is mixed and added into 0.6 gram of pure water to form pastel. About 10 minutes are solidified to obtain a solid material after this pastel is fashioned into a rectangle. After solidification, this hard solids material is placed in air a few hours. Afterwards solid material with pure water lixiviation and is cleaned for several times, and be repeatedly performed this lixiviation with cleaning step until the surface p H of solid material is close to 6 or lower slightly. Biphase ceramics by air-dry for the solid material after this final lixiviation dicalcium phosphate dihydrate Yu oxyhydrogen-base apatite to obtain weight 2.3 grams and density 2.54 grams per milliliter.
Embodiment 5
By 4.2 grams of oxyhydrogen-base apatites (size by 150 order numbers) sintered and 2.1 gram of one water one-lime phosphate (Ca (H2PO4)2��H2O, MCPM) it is mixed and added into 1.65 grams of pure water to form pastel. About 4 minutes are solidified to obtain a solid material after this pastel is fashioned into a rectangle. After solidification, this hard solids material is placed in air 48 hours. Afterwards solid material with pure water lixiviation and is cleaned for several times, and be repeatedly performed this lixiviation with cleaning step until the surface p H of solid material is close to 6 or lower slightly. With reference to Fig. 5, XRD figure spectrum shows the biphase ceramics that this product is DCPD ceramic and oxyhydrogen-base apatite.
Although having shown that and illustrate only certain embodiments of the present invention, but according to the method for teachings of the present invention, the present invention can not necessarily departed from and bigger viewpoint is made an amendment or changed for those of ordinary skill in the art by substantially learning. Therefore, any spirit without departing from the present invention and category, and to its equivalent modifications carried out or change, be intended to be limited solely by appended claims.

Claims (11)

1. the method for the biphase ceramics of the biphase ceramics manufacturing DCPD ceramic, DCPA ceramic, dicalcium phosphate dihydrate and oxyhydrogen-base apatite or anhydrous dicalcium phosphate and oxyhydrogen-base apatite, it is characterised in that its step includes:
Form a mixture, this mixture contains a phosphoric acid or an acid phosphatase salt compound and a basic calcium phosphate compound, wherein, this basic calcium phosphate compound is the oxyhydrogen-base apatite of sintering, and the choosing of this acid phosphatase salt compound freely a water one-lime phosphate, anhydrous phosphoric acid one calcium or its group formed;
Add and add water in this mixture to form a pastel;
Mould this pastel and become a required form, and this pastel that hardens is to obtain a solid material;
Clean and this solid material of lixiviation, until a surface p H of this solid material reaches 4.5 or higher; And
This solid material dry is to obtain the biphase ceramics of DCPD ceramic or dicalcium phosphate dihydrate and oxyhydrogen-base apatite at lower than 95 DEG C, or 100 DEG C or more relative superiority or inferiority dry this solid material to obtain the biphase ceramics of DCPA ceramic or anhydrous dicalcium phosphate and oxyhydrogen-base apatite;
Wherein, when the stoichiometry of this phosphoric acid provided or this acid phosphatase salt compound equals or exceeds the percentage by weight of this basic calcium phosphate compound 0.1% to 20%, then a product is this DCPD ceramic or this DCPA ceramic; When the stoichiometry of this phosphoric acid provided or this acid phosphatase salt compound is less than this basic calcium phosphate compound, this product is the biphase ceramics of this dicalcium phosphate dihydrate biphase ceramics with oxyhydrogen-base apatite or this anhydrous dicalcium phosphate and oxyhydrogen-base apatite.
2. the method for claim 1, it is characterised in that mould and after cure step at this, also includes a step drying this solid material at room temperature to 90 DEG C.
3. the method for claim 1, it is characterised in that this basic calcium phosphate compound has a calcium/phosphorus mol ratio more than 1, this acid phosphatase salt compound then has a calcium/phosphorus mol ratio less than 1.
4. the method for claim 1, it is characterised in that the purity of this DCPD ceramic or this DCPA ceramic is at least 97%.
5. the method for claim 1, it is characterized in that, the biphase ceramics of the biphase ceramics of this DCPD ceramic, DCPA ceramic, dicalcium phosphate dihydrate and oxyhydrogen-base apatite or anhydrous dicalcium phosphate and oxyhydrogen-base apatite is graininess or bulk.
6. method as claimed in claim 5, it is characterized in that, the biphase ceramics of the biphase ceramics of this DCPD ceramic, DCPA ceramic, dicalcium phosphate dihydrate and oxyhydrogen-base apatite or anhydrous dicalcium phosphate and oxyhydrogen-base apatite is particle size range the graininess of 0.1 millimeter to 5 millimeter.
7. method as claimed in claim 5, it is characterized in that, the biphase ceramics of the biphase ceramics of this DCPD ceramic, DCPA ceramic, dicalcium phosphate dihydrate and oxyhydrogen-base apatite or anhydrous dicalcium phosphate and oxyhydrogen-base apatite is the bulk with pore space structure.
8. the method for claim 1, it is characterized in that, this dicalcium phosphate dihydrate and the biphase ceramics of oxyhydrogen-base apatite or the biphase ceramics of anhydrous dicalcium phosphate and oxyhydrogen-base apatite include the dicalcium phosphate mineral of the percentage by weight of 30% to 95% and the oxyhydrogen-base apatite of the percentage by weight of 5% to 70%.
9. the method for claim 1, it is characterised in that this mixture also includes a porogen.
10. method as claimed in claim 9, it is characterised in that this porogen includes sodium chloride, potassium chloride, maltose, sucrose or its combination.
11. a bioceramic for the medical applications for sclerous tissues position, its group formed with the biphase ceramics of oxyhydrogen-base apatite and the biphase ceramics of anhydrous dicalcium phosphate and oxyhydrogen-base apatite selected from the DCPD ceramic manufactured by a method described in claim 1, DCPA ceramic, dicalcium phosphate dihydrate.
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